Aug 2019, Volume 13 Issue 4

Cover illustration

  • The shale oil and gas exploitation consumes substantial amounts of freshwater and generates large quantities of hazardous wastewater. Despite their success in shale oil and gas wastewater treatment at the laboratory scale, membrane technologies have not been implemented at full scale in the oil and gas fields. This article analyzes the growing demands of wastewater treatment in shale oil and gas production, and critically reviews the current stage of membrane technologies app [Detail] ...

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    Longfei Wang, Jiaxin Tong, Yi Li

    The trans-regional characteristics of watershed governance produce more problems beyond the capacity of each individual water-related department, leading to the fragmentation of watershed management. The River Chief System (RCS) has experienced swift developments over the past decade in China by appointing the local government heads as river chiefs. RCS works efficiently in the short-term due to its superiority in the inclusion of clear responsibility, authority, and multi-sectoral collaboration. However, the characteristics of the authority-based vertical coordination of the hierarchical system remain unchanged, and therefore the problems of organizational logic and the responsibility dilemma still exist. Tasks including perfecting of laws, integrated watershed management, and public participation still need to be completed. RCS reflects the routine and characteristics of the migration of national governance, and as such provides new insights for other developing countries in the design of river management systems.

    Tiezheng Tong, Kenneth H. Carlson, Cristian A. Robbins, Zuoyou Zhang, Xuewei Du

    • Shale oil and gas production generates wastewater with complex composition.

    • Membrane technologies emerged for the treatment of shale oil and gas wastewater.

    • Membrane technologies should tolerate high TDS and consume low primary energy.

    • Pretreatment is a key component of integrated wastewater treatment systems.

    • Full-scale implementation of membrane technologies is highly desirable.

    Shale oil and gas exploitation not only consumes substantial amounts of freshwater but also generates large quantities of hazardous wastewater. Tremendous research efforts have been invested in developing membrane-based technologies for the treatment of shale oil and gas wastewater. Despite their success at the laboratory scale, membrane processes have not been implemented at full scale in the oil and gas fields. In this article, we analyze the growing demands of wastewater treatment in shale oil and gas production, and then critically review the current stage of membrane technologies applied to the treatment of shale oil and gas wastewater. We focus on the unique niche of those technologies due to their advantages and limitations, and use mechanical vapor compression as the benchmark for comparison. We also highlight the importance of pretreatment as a key component of integrated treatment trains, in order to improve the performance of downstream membrane processes and water product quality. We emphasize the lack of sufficient efforts to scale up existing membrane technologies, and suggest that a stronger collaboration between academia and industry is of paramount importance to translate membrane technologies developed in the laboratory to the practical applications by the shale oil and gas industry.

    Nan Zhao, Huu Hao Ngo, Yuyou Li, Xiaochang Wang, Lei Yang, Pengkang Jin, Guangxi Sun

    A comprehensive pollutant transformation model for sewer systems is established.

    The model comprises fermentation, sulfate reduction and ammonification processes.

    Biochemical reactions related to distinct carbon sources are depicted in the model.

    Pollutant transformation is attributed to different biochemical reaction processes.

    Presently, several activated sludge models (ASMs) have been developed to describe a few biochemical processes. However, the commonly used ASM neither clearly describe the migratory transformation characteristics of fermentation nor depict the relationship between the carbon source and biochemical reactions. In addition, these models also do not describe both ammonification and the integrated metabolic processes in sewage transportation. In view of these limitations, we developed a new and comprehensive model that introduces anaerobic fermentation into the ASM and simulates the process of sulfate reduction, ammonification, hydrolysis, acidogenesis and methanogenesis in a gravity sewer. The model correctly predicts the transformation of organics including proteins, lipids, polysaccharides, etc. The simulation results show that the degradation of organics easily generates acetic acid in the sewer system and the high yield of acetic acid is closely linked to methanogenic metabolism. Moreover, propionic acid is the crucial substrate for sulfate reduction and ammonification tends to be affected by the concentration of amino acids. Our model provides a promising tool for simulating and predicting outcomes in response to variations in wastewater quality in sewers.

    Gaoling Wei, Jinhua Zhang, Jinqiu Luo, Huajian Xue, Deyin Huang, Zhiyang Cheng, Xinbai Jiang

    • Biochar supported nanoscale zero-valent iron composite (nZVI/BC) was synthesized.

    • nZVI/BC quickly and efficiently removed nitrobenzene (NB) in solution.

    • NB removal by nZVI/BC involves simultaneous adsorption and reduction mechanism.

    • nZVI/BC exhibited better catalytic activity, stability and durability than nZVI.

    The application of nanoscale zero-valent iron (nZVI) in the remediation of contaminated groundwater or wastewater is limited due to its lack of stability, easy aggregation and iron leaching. To address this issue, nZVI was distributed on oak sawdust-derived biochar (BC) to obtain the nZVI/BC composite for the highly efficient reduction of nitrobenzene (NB). nZVI, BC and nZVI/BC were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). For nZVI/BC, nZVI particles were uniformly dispersed on BC. nZVI/BC exhibited higher removal efficiency for NB than the simple summation of bare nZVI and BC. The removal mechanism was investigated through the analyses of UV-Visible spectra, mass balance and XPS. NB was quickly adsorbed on the surface of nZVI/BC, and then gradually reduced to aniline (AN), accompanied by the oxidation of nZVI to magnetite. The effects of several reaction parameters, e.g., NB concentration, reaction pH and nZVI/BC aging time, on the removal of NB were also studied. In addition to high reactivity, the loading of nZVI on biochar significantly alleviated Fe leaching and enhanced the durability of nZVI.

    Shihao Sun, Tipei Jia, Kaiqi Chen, Yongzhen Peng, Liang Zhang

    A two-stage BTF system was established treating odorous off-gas mixture from a WWTP.

    The two-stage BTF system showed resistance for the lifting load of H2S and VOSC.

    Miseq Illumina sequencing showed separated functional microbial community in BTFs.

    Avoiding H2S inhibition and enhancement of VOSC degradation was achieved.

    Key control point was discussed to help industrial application of the system.

    Simultaneous removal of hydrogen sulfide (H2S) and volatile organic sulfur compounds (VOSCs) in off-gas mixture from a wastewater treatment plant (WWTP) is difficult due to the occasional inhibitory effects of H2S on VOSC degradation. In this study, a two-stage bio-trickling filter (BTF) system was developed to treat off-gas mixture from a real WWTP facility. At an empty bed retention time of 40 s, removal efficiencies of H2S, methanethiol, dimethyl sulfide, and dimethyl disulfide were 90.1, 88.4, 85.8, and 61.8%, respectively. Furthermore, the effect of lifting load shock on system performance was investigated and results indicated that removal of both H2S and VOSCs was slightly affected. Illumina Miseq sequencing revealed that the microbial community of first-stage BTF contained high abundance of H2S-affinity genera including Acidithiobacillus (51.43%), Metallibacterium (25.35%), and Thionomas (8.08%). Analysis of mechanism demonstrated that first stage of BTF removed 86.1% of H2S, mitigating the suppression on VOSC degradation in second stage of BTF. Overall, the two-stage BTF system, an innovative bioprocess, can simultaneously remove H2S and VOSC.

    Siyu Chen, Lee Blaney, Ping Chen, Shanshan Deng, Mamatha Hopanna, Yixiang Bao, Gang Yu

    Specific second-order rate constants were determined for 5-FU and CAP with ozone.

    Reaction sites were confirmed by kinetics, Fukui analysis, and products.

    The olefin moiety was the main ozone reaction site for 5-FU and CAP.

    Carboxylic acids comprised most of the residual TOC for 5-FU.

    Ozonation removed the toxicity associated with 5-FU and products but not CAP.

    Anticancer drugs (ADs) have been detected in the environment and represent a risk to aquatic organisms, necessitating AD removal in drinking water and wastewater treatment. In this study, ozonation of the most commonly used antimetabolite ADs, namely 5-fluorouracil (5-FU) and its prodrug capecitabine (CAP), was investigated to determine reaction kinetics, oxidation mechanisms, and residual toxicity. The specific second-order rate constants between aqueous ozone and 5-FU, 5-FU, 5-FU2, CAP, and CAP were determined to be 7.07(±0.11)×104 M1·s1, 1.36(±0.06)×106 M1·s1, 2.62(±0.17)×107 M1·s1, 9.69(±0.08)×103 M1·s1, and 4.28(±0.07)×105 M1·s1, respectively; furthermore, the second-order rate constants for OH reaction with 5-FU and CAP at pH 7 were determined to be 1.85(±0.20)×109 M1·s1 and 9.95(±0.26)×109 M1·s1, respectively. Density functional theory was used to predict the main ozone reaction sites of 5-FU (olefin) and CAP (olefin and deprotonated secondary amine), and these mechanisms were supported by the identified transformation products. Carboxylic acids constituted a majority of the residual organic matter for 5-FU ozonation; however, carboxylic acids and aldehydes were important components of the residual organic matter generated by CAP. Ozone removed the toxicity of 5-FU to Vibrio fischeri, but the residual toxicity of ozonated CAP solutions exhibited an initial increase before subsequent removal. Ultimately, these results suggest that ozone is a suitable technology for treatment of 5-FU and CAP, although the residual toxicity of transformation products must be carefully considered.

    Chunhong Chen, Hong Liang, Dawen Gao

    AOA amoA genes in the soils of the two wetlands affiliated with three lineages.

    The main drivers of AOA community were pH and total organic carbon and ammonium.

    The soil characteristics rather than the vegetation control the AOA community.

    Since its first detection, ammonia-oxidizing archaea (AOA) have been proven to be ubiquitous in aquatic and terrestrial ecosystems. In this study, two freshwater marsh wetlands- the Honghe wetland and Qixinghe wetland – in the black soil zone in North-east China were chosen to investigate the AOA community diversity and distribution in wetland soils with different vegetation and depth. In the Honghe wetland, two sampling locations were chosen as the dominant plant transited from Deyeuxia to Carex. In the Qixinghe wetland, one sample location that was dominated by Deyeuxia was chosen. Samples of each location were collected from three different depths, and Illumina MiSeq platform was used to generate the AOA amoA gene archive. The results showed that the AOA amoA genes in the soils of the two wetlands were affiliated with three lineages: Nitrososphaera, Nitrosotalea, and Nitrosopumilus clusters. The different dominant status of these AOA lineages indicated their differences in adapting to acidic habitat, oxygenic/hypoxic alternation, organic matter, and other environmental factors, suggesting high diversity among AOA in marsh soils. The main driver of the AOA community was pH, along with organic carbon and ammonium nitrogen, which also played an important role combined with many other environmental factors. Thus, soil physiochemical characteristics, rather than vegetation, were the main cause of AOA community diversity in the wetlands in the black soil zone in China.

    Victor M. Deantes-Espinosa, Tian-Yuan Zhang, Xiao-Xiong Wang, Yinhu Wu, Guo-Hua Dao, Hong-Ying Hu

    Attachment of Scenedesmus sp. LX1 was tested on certain materials.

    A criterion for selection of materials was used to choose seven materials.

    The amount of S. sp. LX1 attached on polyurethane foam was 51.74 mg/L.

    Materials’ surface influenced the attachment of microalgae.

    Hydrophilic and hydrophobic properties also affected the attachment of S. sp. LX1.

    Attached cultivation systems in the literature do not present a methodology to screen materials for microalgal growth. Hence, a method is needed to find suitable materials for attached cultivation that may enhance attachment of microalgae. In this paper, we have tested seven materials culturing Scenedesmus sp. LX1 (S. sp. LX1) to evaluate the attachment of microalgae on the material surface, its growth in suspension phase and the properties of the materials. Two materials showed attachment of S. sp. LX1, polyurethane foam and loofah sponge, and allowed microalgae to grow both in the surface of the material and suspended phase. Polyurethane foam proved to be a good material for attachment of S. sp. LX1 and the amount of attached microalgae obtained was 51.73 mg/L when adding 100 pieces/L. SEM images showed that the surface and the pore size of the materials affected the attachment of the microalgae, increasing its attachment in scaffold-like materials. Furthermore, the hydrophilic and hydrophobic properties of the materials also affected the attachment of microalgae. This research can be used as a methodology to search for the assessment of a material suitable for attachment of microalgae.

    Peng Hu, Changsheng Guo, Yan Zhang, Jiapei Lv, Yuan Zhang, Jian Xu

    We developed a method for determining 11 abused drugs in water and sediment.

    METH and EPH were the dominant drugs in water and sediment in Beiyunhe River.

    Abuse drugs in Beiyunhe River were mainly from hospitals and sewage effluents.

    Abused drugs in the water would not impair the aquatic ecosystem biologically.

    This study investigated the presence of 11 abused drugs and their metabolites, including amphetamine, methamphetamine (METH), ketamine, ephedrine (EPH), cocaine, benzoylecgonine, methadone, morphine, heroin, codeine, and methcathinone in the surface water and sediment samples of Beiyunhe River, a typical urban river flowing through Beijing, Tianjin, and Hebei provinces in North China. An analytical method of determining these abused drugs and their metabolites in water and sediment was developed and validated prior to sample collection in the study area. Results showed that METH and EPH were predominant in water and sediment samples. The total drug concentrations ranged from 26.6 to 183.0 ng/L in water and from 2.6 to 32.4 ng/g dry weight in sediment, and the drugs mainly originated from hospitals and sewage treatment plants. The average field-based sediment water distribution coefficients of abused drugs were calculated between 149.3 and 1214.0 L/kg and corrected by organic carbon. Quotient method was used to assess the risks. The findings revealed that these drugs and their metabolites at determined concentrations in water samples will not impair the aquatic ecosystem biologically, but their potential harmful effect on the function of the ecosystem and human health should not be overlooked.

    Xuehao Zhao, Yinhu Wu, Xue Zhang, Xin Tong, Tong Yu, Yunhong Wang, Nozomu Ikuno, Kazuki Ishii, Hongying Hu

    Humic acids (HA) didn’t cause obvious reverse osmosis (RO) membrane fouling in 45 h.

    Osmotic pressure (NaCl) affected slightly the RO membrane fouling behavior of HA.

    Ca2+ promoted aggregation of HA molecules and thus aggravated RO membrane fouling.

    Ozonation eliminated the effect of Ca2+ on the RO membrane fouling behavior of HA.

    The change of the structure of HA was related to its membrane fouling behavior.

    Humic acid has been considered as one of the most significant sources in feed water causing organic fouling of reverse osmosis (RO) membranes, but the relationship between the fouling behavior of humic acid and the change of its molecular structure has not been well developed yet. In this study, the RO membrane fouling behavior of humic acid was studied systematically with ozonation as a pretreatment method to control RO membrane fouling. Furthermore, the effect of ozone on the structure of humic acid was also explored to reveal the mechanisms. Humic acid alone (10–90 mg/L, in deionized water) was found not to cause obvious RO membrane fouling in 45-h operation. However, the presence of Ca2+ aggravated significantly the RO membrane fouling caused by humic acid, with significant flux reduction and denser fouling layer on RO membrane, as it was observed by scanning electron microscope (SEM) and atomic force microscope (AFM). However, after the pretreatment by ozone, the influence of Ca2+ was almost eliminated. Further analysis revealed that the addition of Ca2+ increased the particle size of humic acid solution significantly, while ozonation reduced the SUVA254, particle size and molecular weight of the complexes of humic acid and Ca2+ (HA-Ca2+ complexes). According to these results and literature, the bridge effect of Ca2+ aggregating humic acid molecules and the cleavage effect of ozone breaking HA-Ca2+ complexes were summarized. The change of the structure of humic acid under the effect of Ca2+ and ozone is closely related to the change of its membrane fouling behavior.

    Zhiqiang Chen, Lizhi Zhao, Ye Ji, Qinxue Wen, Long Huang

    Effect of nitrogen on mixed culture PHA production was reconsidered.

    Enrichment history of PHA accumulating culture was discussed.

    Higher PHA content and biomass growth were achieved in presence of nitrogen.

    Enrichment strategy toward higher PHA accumulation was investigated.

    Microbial community succession in PHA accumulation phase was investigated.

    In most of the operating strategies for mixed microbial cultures polyhydroxyalkanoate (PHA) production, moderate organic loads and low nitrogen concentrations are used, however, the real waste streams contain variable concentrations of carbon and nitrogen. To evaluate the effect of enrichment history on PHA producer and production the various carbon and nitrogen levels were utilized during the accumulation phase. Different operating strategies were applied in three sequencing batch reactors (SBRs) subjected to aerobic dynamic feeding. The maximum PHA production of the enriched cultures under nutrient excess, limitation and starvation (Cmol/Nmol ratio of 8, 40 and ∞, respectively) was evaluated in batch assays. A higher PHA content and biomass growth were achieved in the nutrients presence in comparison to the nutrient starvation condition. The cultures from the SBR treated under short sludge retention time, high organic loading rate, short cycle length (SBR#3) and nutrient excess reached the maximum PHA content (54.9%) and biomass increase (38.9%). Under nutrient limitation, the negative biomass growth was observed under nutrient starvation because of the sampling loss. The succession of microbial communities in SBRs and batch assays was analyzed using terminal restriction fragment length polymorphism. The SBR#3 had the best overall PHA production performance considering its high PHA content and productivity in all nutrient content, it indicates that nitrogen has a substantial impact on PHA yield especially when high organic loading rate enrichment history is involved.

    Xiaoxue Mei, Heming Wang, Dianxun Hou, Fernanda Leite Lobo, Defeng Xing, Zhiyong Jason Ren

    Reveals the synergy between microbial fuel cells and electrocoagulation.

    Demonstrates MFC-ECC shipboard wastewater treatment is advantageous.

    MFC-ECC integration enables energy neutral bilge water treatment.

    Ships generate large amounts of wastewater including oily bilge water, blackwater and greywater. Traditionally they are treated separately with high energy consumption. In this study we demonstrate the feasibility that these waste streams can be treated using an integrated electrocoagulation cell (ECC) and microbial fuel cell (MFC) process, which not only synergized the contaminants removal but also accomplished energy neutrality by directly powering EC with MFC electricity. Results showed that MFC stack powered ECC removed 93% of oily organics, which is comparable to the performance of an external DC voltage powered ECC. In the meantime, more than 80% of COD was removed from MFCs when fed with either acetate or municipal wastewater. Moreover, the ECC electrode area and distance showed notable effects on current generation and contaminants removal, and further studies should focus on operation optimization to enhance treatment efficiency.

    Zhenfeng Han, Ying Miao, Jing Dong, Zhiqiang Shen, Yuexi Zhou, Shan Liu, Chunping Yang

    Anaerobically digested swine wastewater was treated by a novel constructed wetland.

    Tidal operation was better for total nitrogen removal than intermittent flow.

    Mechanism of nitrogen removal by biozeolite-based constructed wetland was discussed.

    Simultaneous nitrification and denitrification were determined in zeolite layer.

    Nitrogen removal of wastewater containing high-strength ammonium by the constructed wetlands (CWs) has been paid much attention. In this study, the ability of a partially saturated CW to treat anaerobically-digested decentralized swine wastewater under varying operating parameters from summer to winter was investigated. The partially saturated CW achieved better NH4+-N and TN removal by tidal flow than intermittent flow. With surface loading rates of 0.108, 0.027, and 0.029 kg/(m2·d) for COD, NH4+-N, and TN, the partially saturated CW by tidal operation achieved corresponding removal efficiencies of 85.94%, 61.20%, and 57.41%, respectively, even at 10°C. When the rapid-adsorption of NH4+-N and the bioregeneration of zeolites reached dynamically stable, the simultaneous nitrification and denitrification in the aerobic zeolite layer was observed and accounted for 58.82% of the total denitrification of CW. The results of Illumina high-throughput sequencing also indicated that nitrifiers (Nitrospira and Rhizomicrobium) and denitrifiers (Rhodanobacter and Thauera) simultaneously existed in the zeolite layer. The dominant existence of versatile organic degraders and nitrifiers/denitrifiers in the zeolite layer was related to the removal of most COD and nitrogen in this zone. The contribution of the possible nitrogen removal pathways in the CW was as follows: nitrification-denitrification (86.55%)>substrate adsorption (11.70%)>plant uptake (1.15%)>microbial assimilation (0.60%).

    Xiaomeng Wang, Ning Li, Jianye Li, Junjun Feng, Zhun Ma, Yuting Xu, Yongchao Sun, Dongmei Xu, Jian Wang, Xueli Gao, Jun Gao

    RSM was utilized to optimize and model influential parameters on fluoride removal.

    Regression models involving independent variables and main response were developed.

    Interactive effects and optimum of process factors were illuminated and determined.

    Fluoride removal efficiency of 99.69% was observed in optimal process conditions.

    Response surface methodology was utilized to model and optimize the operational variables for defluoridation using an electrodialysis process as the treatment of secondary effluent of the graphite industry. Experiments were conducted using a Box-Behnken surface statistical design in order to evaluate the effects and the interaction of the influential variables including the operational voltage, initial fluoride concentration and flow rate. The regression models for defluoridation and energy consumption responses were statistically validated using analysis of variance (ANOVA); high coefficient of determination values (R2 = 0.9772 and R2 = 0.9814; respectively) were obtained. The quadratic model exhibited high reproducibility and a good fit of the experimental data. The optimum values of the initial fluoride concentration, voltage and flow rate were found to be 13.9 mg/L, 13.4 V, 102.5 L/h, respectively. A fluoride removal efficiency of 99.69% was observed under optimum conditions for the treatment of the secondary effluent of the graphite industry.

    Chao Pang, Chunhua He, Zhenhu Hu, Shoujun Yuan, Wei Wang

    The existence of three-phase separator did not affect COD removal in the EAnCMBR.

    The existence of three-phase separator aggravated methane leakage of EAnCMBR.

    The existence of three-phase separator aggravated membrane fouling rate of EAnCMBR.

    Start-up of EAnCMBR equipped three-phase separator was slightly delayed.

    The three-phase separator is a critical component of high-rate anaerobic bioreactors due to its significant contribution in separation of biomass, wastewater, and biogas. However, its role in an anaerobic membrane bioreactor is still not clear. In this study, the distinction between an external anaerobic ceramic membrane bioreactor (EAnCMBR) unequipped (R1) and equipped (R2) with a three-phase separator was investigated in terms of treatment performance, membrane fouling, extracellular polymers of sludge, and microbial community structure. The results indicate that the COD removal efficiencies of R1 and R2 were 98.2%±0.4% and 98.1%±0.4%, respectively, but the start-up period of R2 was slightly delayed. Moreover, the membrane fouling rate of R2 (0.4 kPa/d) was higher than that of R1 (0.2 kPa/d). Interestingly, the methane leakage from R2 (0.1 L/d) was 20 times higher than that from R1 (0.005 L/d). The results demonstrate that the three-phase separator aggravated the membrane fouling rate and methane leakage in the EAnCMBR. Therefore, this study provides a novel perspective on the effects of a three-phase separator in an EAnCMBR.

    Huosheng Li, Hongguo Zhang, Jianyou Long, Ping Zhang, Yongheng Chen

    Addition of alkali to pH 10 is effective for precipitation of precipitable metals.

    Fenton treatment is effective for substantial removal of Tl, Cd, Cu, Pb, and Zn.

    Sulfide precipitation is a final step for removal of trace Tl, Cd, Cu, Pb, and Zn.

    Bench and pilot studies demonstrated the effectiveness of this combined technique.

    Thallium (Tl) in industrial wastewater is a public health concern due to its extremely high toxicity. However, there has been limited research regarding Tl removal techniques and engineering practices to date. In this investigation, bench and pilot studies on advanced treatment of industrial wastewater to remove Tl to a trace level were conducted. The treatment process involved a combination of hydroxide precipitation, Fenton oxidation, and sulfide precipitation. While hydroxide precipitation was ineffective for Tl+ removal, it enabled the recovery of approximately 70%–80% of Zn as Zn hydroxide in alkaline conditions. The Fenton process provided good Tl removal (>95%) through oxidation and precipitation. Tl was then removed to trace levels (<1.0 µg/L) via sulfide precipitation. Effective removal of other heavy metals was also achieved, with Cd<13.4 µg/L, Cu<39.6 µg/L, Pb<5.32 µg/L, and Zn<357 µg/L detected in the effluent. X-ray photoelectron spectroscopy indicated that Tl2S precipitate formed due to sulfide precipitation. Other heavy metals were removed via the formation of metal hydroxides during hydroxide precipitation and Fenton treatment, as well as via the formation of metal sulfides during sulfide precipitation. This combined process provides a scalable approach for the in-depth removal of Tl and other heavy metals from industrial wastewater.